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951.
This paper brings a new rigorous and complete statistical approach to the data processing of the mobility curves of univalent weak bases. This approach is based on application of the least square method to the equation of the related mobility curve. Thus, an equation for the best fit is derived and its mathematical solution is found. The solution brings best estimates of the mobility curve parameters, i.e., dissociation constant K and ionic mobility of the protonated base U. Further, explicit formulas have been derived for the calculation of related statistical parameters, i.e., SDs of effective mobility s(u), of the dissociation constant s(K), and of ionic mobility of protonated base s(U). The mathematical functions used in the above approach do not impose any limitations on the data used, i.e., the mobility and pH values used may be real numbers (positive, negative, zero). 相似文献
952.
Candiano G Santucci L Petretto A Pavone B Del Boccio P Musante L Bruschi M Federici G Gusmano R Urbani A Ghiggeri GM 《Electrophoresis》2008,29(3):682-694
A 2-DE system has been devised in which proteins are first separated in their native state followed by separation according to mass under denaturing conditions (Nat/SDS-PAGE). Hydrophilic properties of the gel and the presence of dihydroxybisacrylamide in the first dimension allowed a good resolution for high-molecular-weight proteins and maintained interactions. With this method 252 plasma spots have been resolved and 140 have been characterized by MS as isoforms of 60 proteins, a relevant part of which (12) were not detected by traditional 2-D gels or by other nondenaturing 2-D techniques. The list includes complement factors (C4d, C7), coagulation factors (coagulation factor II, fibrin beta), apolipoproteins (apolipoprotein B) and cell debris (vinculin, gelsolin, tropomyosin, dystrobrevin beta, fibrinectin I). Nat/SDS PAGE also allowed separation of nicked forms of albumin, Apo B100 and alpha2-macroglobulin and showed the presence of atypical albumin adducts corresponding to post-translational and oxidation products. Our system provides therefore new tools for resolving proteins, protein aggregates and complexes and amplifies the potentiality of traditional electrophoretic analysis. 相似文献
953.
954.
Somma A Ferranti P Addeo F Mauriello R Chianese L 《Journal of chromatography. A》2008,1192(2):294-300
The main peptides produced by hydrolysis of water buffalo beta-casein with plasmin were characterized by capillary electrophoresis and mass spectrometry and compared with their bovine homologous. A novel breakdown product arising from the hydrolysis of water buffalo beta-casein, originated by the presence of a plasmin-sensitive Lys bond at position 68 was identified, which was not present in bovine beta-casein. On the basis of this evidence, an improved procedure for the detection and the differentiation of the products of plasmin hydrolysis of bovine and water buffalo beta-casein by capillary isoelectric focusing was set-up. In the experimental conditions, the gamma-casein from the two species was efficiently separated. Comparison of the capillary electropherograms with those obtained by ultra-thin-layer isoelectric focusing, the reference method for routine analysis of plasmin digests of casein, suggests that capillary electrophoresis isoelectric focusing may constitute a successful alternative to the traditional slab gel electrophoresis analysis of plasmin digests of casein either for basic structural studies or for applications in the quality assessment of dairy products. 相似文献
955.
A 4-component Ugi reaction with a suitable isocyanide, followed by a novel secondary transformation involving a Pd(II)-mediated (R5 = H) or a Pd(0)-mediated (R5 = CO2Me) SN2' cyclization to give highly functionalized N-acyl-2-vinylpyrrolidines, is reported. The overall yields are usually good and in most cases the Pd(0)-catalyzed reaction gave the final product in almost quantitative yield. 相似文献
956.
Capriati V Florio S Luisi R Mazzanti A Musio B 《The Journal of organic chemistry》2008,73(8):3197-3204
The alpha-lithiation-trapping sequence of trans-N-alkyl-2,3-diphenylaziridines (s-BuLi or s-BuLi/TMEDA), taking place with a stereochemistry which dramatically depends on the solvent coordinating ability (inversion of configuration in THF and retention in toluene), has been carefully investigated. 1H,13C, and 7Li multinuclear NMR investigations at low temperature suggest that two differently configured lithiated aziridines (monomeric cis-1-Li in THF and dimeric trans-1-Li in toluene) are involved. 相似文献
957.
Ressurreição AS Bordessa A Civera M Belvisi L Gennari C Piarulli U 《The Journal of organic chemistry》2008,73(2):652-660
A practical synthesis of a new bifunctional diketopiperazine (DKP) scaffold 1, formally derived from the cyclization of L-aspartic acid and (S)-2,3-diaminopropionic acid, is reported. DKP-1 bears a carboxylic acid and an amino functionalities in a cis relationship, which have been used to grow peptide sequences. Tetra-, penta-, and hexapeptidomimetic sequences were prepared by solution-phase peptide synthesis (Boc strategy). Conformational analysis of these derivatives was carried out by a combination of 1H NMR spectroscopy, IR spectroscopy, CD spectroscopy, and computer modeling, and reveals the formation of beta-hairpin mimics involving 10-membered and 18-membered H-bonded rings and a reverse turn of the growing peptide chain. 相似文献
958.
Bazzicalupi C Bencini A Bianchi A Borri C Danesi A Garcia-España E Giorgi C Valtancoli B 《The Journal of organic chemistry》2008,73(21):8286-8295
The interaction of the biologically relevant anions deriving from the six pyridinedicarboxylic acids (H2PDC) with two macrocyclic receptors containing a pentamine chain and a bipyridine (1) or a phenanthroline (2) moiety, as well as with the aliphatic analogue [21]aneN7 (3), was studied by means of spectroscopic methods (UV-vis, NMR) and potentiometric titrations affording the stability constants of the adducts formed. All three receptors form stable complexes with the substrates thanks to the formation of several salt bridges and hydrogen bond contacts, as observed in the crystal structure of the H8[3(2,6-PDC)4] x H2O x 0.5 EtOH solid compound. Additional pi-stacking interactions between the aromatic moieties of substrates and receptors enhance the stability of complexes with 1 and 2. Compounds 1 and 2 show a marked selectivity toward 2,6-pyridinedicarboxylate anions. In particular, 1 is able to perform a very efficient recognition of these species in the presence of 2 and 3. Molecular modeling calculations suggested that such recognition ability of 1 can be ascribed to a superior structural and electrostatic complementarity with the substrate compared to 2 and 3. 相似文献
959.
The complexation of Al(III) with d-gluconic acid was studied in solution by means of pH-potentiometry, ESI mass spectrometry and one- and two-dimensional NMR spectroscopy. Six complexes were found to form in solution from pH 2 to 10: [AlL]2+, [AlLH−1]+, [AlLH−2], [AlLH−3]−, [AlL2H−1] and [AlL2H−2]−. NMR spectroscopy indicated very complicated chemical exchange processes between the free ligand and gluconic acid molecules bound in the metal complexes, with different coordination modes resulting in changes both of the chemical shift and of the line shape of the signals. A solid complex [AlL2H−1] · 2H2O was isolated as a microcrystalline powder and characterized. The structures of the complexes are discussed on the basis of the spectroscopic results and MM force field calculations. 相似文献
960.
Ivan Zuliani Andrea Fattori Rossella Svigelj Nicolò Dossi Cristian Grazioli Gino Bontempelli Rosanna Toniolo 《Electroanalysis》2023,35(2):e202200150
A convenient assembly recently proposed for screen printed gold electrodes (SPEs) suitable for measurements in gaseous samples is here tested for the analysis of the ethanol content in alcoholic drinks. This assembly involves the use of a circular crown of filter paper, soaked in the room temperature ionic liquid (RTIL) 1-butyl-3-methylimidazolium hydrogen sulfate, which is simply placed upon a disposable screen printed cell, so as to contact the outer edge of the gold disc working electrode, as well as peripheral counter and reference electrodes. The electrical contact between the paper crown soaked in RTIL and the SPE electrode is assured by a gasket and all components are installed in a polylactic acid holder. This assembly provides a portable and disposable electrochemical platform, assembled by the easy immobilization onto a porous and inexpensive supporting material such as paper of a RTIL characterized by profitable electrical conductivity and negligible vapor pressure. The electroanalytical performance of this device was assayed for the flow injection analysis of the ethanol concentration in some real samples of wine and beer and the results obtained are compared with the alcoholic degree reported in the relevant bottle-labels, thus highlighting a substantially satisfactory agreement. Repeatable sharp peaks (RSD=6–8 %) were detected for ethanol over a wide linear range (1–20 % v/v in water) and a detection and quantitation limit of 0.55 % v/v and 1.60 % v/v were inferred for a signal-to-noise ratio of 3 and 10, respectively. 相似文献